“Chemical Personality of Fluorinated Organics or Why Chemical Architecture
Matters!"
Scott Mabury et alDepartment of Chemistry
University of TorontoFluoros August, 2005
F F
F F
F F
F F
F F
F F
FF
FS
FF
C
F F
F F
F F
F F
F F
F F
FF
F
PFOA
O
O-
PFOS
O
O O-
CO
OF3C
Cl
CH3
FF
FFTefluthrin
Items in Talk ~Items in Talk ~
•• ““NaturalNatural”” OrganofluorinesOrganofluorines
•• Pesticides, Pharmaceuticals, Consumer, Industrial materialsPesticides, Pharmaceuticals, Consumer, Industrial materials
•• Fluorine and the CFluorine and the C--F bondF bond
•• Reactivity ~ oxidation, photolysis, hydrolysis, elimination, meReactivity ~ oxidation, photolysis, hydrolysis, elimination, metabolismtabolism
•• Physical PropertiesPhysical Properties……water solubility, partitioning, volatilitywater solubility, partitioning, volatility
•• Summary with Summary with ‘‘big picturebig picture’’ on PFOS and PFOAon PFOS and PFOA
C CO
OHH
FH
"Fluoroacetate"
OHO
F
Oleic, stearic, palmitic, mystic, etc
Organofluorines =~30; Cl=2,400; Br=2,050
Most Common
F- F2 + 2e (E0 = -3.06V)H2O2 + 2H+ 2e 2H2O (E0 = +1.71V)
[Cl- E0=-1.36V; Br- E0=-1.07]
C CO
SCoA HOOC COOH
OFH H
'Fluorocitrate'inhibit s cit rate t ransport
Highly Toxic
Haloperoxidase?
Natural Organic Fluorines?
C CO
OH
HF
H"Fluoroacetate"
OS+
HO OH
H3CN
N
N
N
NH2-OO
+H3N
S-adenosylmethionine
F- O
HO OH
N
N
N
N
NH2
F
Fluorinase
5'-FDA
C CO
H
HF
HFluoroacetaldehyde
?
O'Hagan et al, 2002, Nature, 416, p279.
Biosynthesis of Fluoroacetate
Aluminum Production: CF4 (82), CF3CF3 (3) [0.75 and 0.11 kg/ton of Al]Freons: CFCl3 (267), CF2Cl2 (535), CF2ClCFCl2 (85)HCFC: CF3CFH2 (12), CHF2Cl (145), CH3CF2Cl (15)HFCs: CF3CHFCF3, CF3CHFCHFCF2CF3, CH2FCF2CHF2
Note: numbers in (x) reflect atmospheric concentration pptv;
IPCC Climate Change 2001: The Scientific Basis
CF4, CF2Cl2, CFCl3, CF3Cl, CHF3, CF2=CF2 (fluorite)1....CFCl3, CF2Cl2, CF2=CF2, CHF2Cl, CHFCl2, CCl2FCClF2 (volcanoes)2...CF3COOH ....estimate of 268 million tons in the world's oceans3; (ocean vents4) 1) Harnisch & Eisenhauer, 1998; Harnischs et al, 2000.
2) Isidorov et al 1990; Isidorov, 1990.3) Frank et al, 20024) Scott et al, 2005
Anthropogenic 'small organofluorines'
Natural Sources as well?
“Small Polyfluorinated Organics”
CF3
NO2O2NN(CH2CH2CH3)2
F3C
HNC
NO
CH3H3C
F3C
O NCH3
HH Cl-+
CF3NO2
OH
CF
F
O
NCO
N
Cl
H H
CO
OF3C
Cl
CH3
FF
FFN
FOH
O O
NN
H3CO
CH3
N
F
OHO
O
O
O
Pesticides and Pharmaceuticals…
CO
H2CCH2
O
Urethane
H2C
H2CCH2
OHN
OCH2
H2C
C O
Ester
CH2CH2OHR
R=CF2CF2CF2CF2CF2CF2CF2CF3
N(CH3)SO2CF2CF2CF2CF2CF2CF2CF2CF3
Ether
R RR
CH2H2C
R
OCH2
H2CR
P ORxOOH
SO OO
Sulfonates (via sulfide) Phosphates
CH2C
R
OHO
Carboxylates
Some Linkages...
in Polymers
Polyfluorinated long alkyl chain materials…
Major Routes to Perfluoro Chains
C8F17SO3-
C8F17SO2F
C8F17SO2N
C8H17SH
C8H17SO2F
PFOSF(CF2CF2)nCH2CH2OH
F(CF2CF2)nCH2CH2I
Sales Products
+
IF5, 2I2; SbF3
Catalysts
TelogenTaxogen
Hydrolysis
CF3CF2(CF2CF2)nI
[adapted from Kissa]
CF2=CF2 CF3CF2I
CF2=CF2
CH2CH2
CH2CH2OH
CH3
Electrochemical
Sales Products
C7F15COO-
PFOA
TelomerizationElectrochemical Fluorination
22,000 liters of AFFF; ~300 kg of PFOS!
“Airport Foam Seeps into Creek”Toronto Star, June 10, 2000
PTFE Leaching of PFOA
Direct releases of Perfluorinated Acids?
PTFE Thermolysis Products
Ellis, D.A., S.A. Mabury, J. Martin, and D.C.G. Muir. 2001. Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment. Nature. 412:321-324; Ellis, DA, JW Martin, DCG Muir, and SA Mabury. 2003. The Use of 19F NMR and Mass Spectrometry for the Elucidation of Novel Fluorinated Acid and Atmospheric Fluoroacid
Precursors Evolved in the Thermolysis of Fluoropolymers. Analyst. 128:756 – 764.
Nomenclature for Fluorinated Polymers
n
FF
FF
FF
FF
FF
FF
FF
F
free-radicalpolymerization
S
"Fluoro- Monomer"
F
"Fluorinated Polymer"
+
F
Esterification
CCH
H
C
H3C
O
HO
OCO
C CH
HH3C
OCO
CCH3
CH2 C
"Monomer"
H2CCH2
H2CO
COC C
H
HH3C
(CH2)xH3C
C
CH3
OO
CH2
m
"Residual Fluoro-alcohol"OO
NH3C CH2
H2COH
"MethyFose Alcohol"
FF
FF
FF
FF
FF
FF
FF
F
S
FF OO
NH3C CH2
H2C
FF
FF
FF
FF
FF
FF
F
FF
S
FF
O
O
NH3C
CH2H2COH F
F
FF
FF
FF
FF
FF
FF
F
S
FF OO
NH3C CH2
H2CH2C
CH2
H2C(CH2)x
H2CCH3
Fluoro alcohols ~ Fugitive Emissions from Residual Material OR Does the Linkage Chemistry Break?
*Dupont Presentation toUSEPA OPPT. Jan 31, 2005US Public Docket AR226-1914
11 to 14 x106 kg/yr (2004)40% in North America80% are in polymers*
Carpet Treatment
Polymer
Potential Sources?
Degradation
N C
FF
FF
FF
FF
FF
FF
FF
F
CH2H2C
OH
FF
F F
F F
F F
F F
F F
F F
FF
FC
F FC
OHH H
H H
FF
FF
FF
FF
FF
FF
FF
F
CH2H2C
FF
OO
OO
FF
FF
FF
FF
FF
FF
FF
F
CH2H2C
FF
O
FF
FF
FF
FF
FF
FF
FF
F
Urethane EtherEster
CH2H2C
FF
Residual
Posters: ENV004, 018, 023Posters: ENV004, 018, 023
Fluorinated Material Dry Weight % Residual
Polyfox-L-DiolTeflonTM AdvanceZonylTM FSO 100ZonylTM FSE8:2 Methacrylate MonomerMotomasterTM Windshield Washer Fluid w/ Teflon
ScotchgardTM Rug and Carpet Protector*
0.11 (0.03)0.34 (0.20)1.03 (0.61)3.80 (1.09)0.04 (0.01)0.36 (0.01)
0.39 (0.06)
C
C
FF
F
CO
HF
HH
HH
FF
F x = 2 to 10FTOH
n=3 or 6 DinglasanDinglasan, MJA and SA Mabury. 2005. , MJA and SA Mabury. 2005. Environ. Sci. Technol. In review
Residuals could be important source of Residuals could be important source of fluoroalcoholsfluoroalcohols……to the atmosphereto the atmosphere
CC
F F F F F FF F F F F FF F F F F F F F F F F F
FF F F F F F F F F FF F F F F F F F F FF
F
FOH
H H
H H 24:2 FTOH"49 Fluorines"
Tentatively identified in a telomer phosphate mixture via GC/MS;Tentatively identified in a telomer phosphate mixture via GC/MS; see see Poster ANA044Poster ANA044
bond length C-X (A)
1.09
1.39
1.78
1.93
EN
2.2
4.0
3.0
2.8
Bond Strength C-X (kcal/mol)
99
110
85
71
H
F
Cl
Br
Van der Waal's radius (A)
1.20
1.35
1.80
1.95
Hydradation X-
(kcal/mol)
-
117
84
78
C Fδ−δ+
Anything Interesting about the CAnything Interesting about the C--F bond?F bond?
f(x)
0.094
0.38
0.28
0.071
3.4
F
Cl
Br
CF3
OH
X
H2C Xδ−δ+
H •O H
H2C Fδ−δ+
H
H2C CH2
FH
C C OHH H
HHCF
FR
Rxn
What does the Fluorine atom do to reactivity What does the Fluorine atom do to reactivity towards Oxidation?towards Oxidation?
Slows it way down!Slows it way down!
NoteNote: Similar story for ring: Similar story for ringoxidations.oxidations.
Kwok & Atkinson; 1995; Kwok & Atkinson; 1995; AtmoAtmo EnvEnv. 29:1685. 29:1685--1695.1695.
•O H
C FF
FH
Lifetime = 260 years!
C FF
FF
Lifetime =>50,000 years!
Slow!
•O HNo Reaction
HFCsHFCs are sloware slow……PFCsPFCs are like diamonds!are like diamonds!
C FF
FF
Lifetime =>50,000 years! Ultimate Fate? Photolysis in upperatmosphere (highly energertic photons)
C•F
FF + F•
Does F• cause O3 destruction like Cl or Br? NO! [104 less than Cl]
F + O2 FO2 (eq far to the right)M
FO2 + O3 FO + 2O2 (very slow)
F + CH4 HF + CH3 (very fast)
F + H2O HF + OH (very fast; exothermic!)
hν
(<210 nm)
Why?
Only option is photolysisOnly option is photolysis……but where?but where?
way up high!way up high!
Wavenumber (cm-1)
800 1000 1200 1400
Rad
ianc
e (1
0-3W
m-2
(cm
-1)-1
)
0
20
40
60
80
100
O3
CO2
CH4H2O
Atmospheric Window
F3C CF3
Lifetime = 10,000 yrsRadiative Efficiency = 0.26 W m-2 ppb-1 GWP (100 yr) = 11,900 (where CO2 = 1)Year 2000 concentration: 3 pptv
IR Transm
ittanceIR
Transmittance
Any problems percolating way up there?Any problems percolating way up there?
Wavenumber (cm-1)
800 1000 1200 1400
σ (1
0-17 cm
2 mol
ecul
e-1)
0.0
0.2
0.4
0.6
0.8
1.0
Rad
ianc
e (1
0-3W
m-2
(cm
-1)-1
)*
0
20
40
60
80
Gal70 H-Gal 1040xAtmospheric Window*
* Calculated for mid-altitude during winter using calculator found on http://geosci.uchicago.edu/~archer/cgimodels/radiation.html
σσ(10(10
-- 1717cmcm33m
oleculem
olecule-- 11
Posters: ENV025 & ANA030Posters: ENV025 & ANA030
F3C O CF
CF3
CF2 OCF2 OCF3
F5S CF3
Lifetime = >1,000 yrsRadiative Efficiency = 0.59 W m-2 ppb-1 GWP (100 yr) = >17,500 (where CO2 = 1)Year 2000 concentration: 4 pptv(Sturges et al, 2000, Science 289:611-613)
R(N, O etc)
CF3
R(N, O etc)
CO
F
R(N, O etc)
CO
OH
-2 F- F-
hν
Photolysis in Natural Waters
H2O
F3C
O NCH3
HH Cl-+
HOOC
O NCH3
HH Cl-+
+ 3 F-
hν
Prozac
R(N, O etc)
F
R(N, O etc)
OH
hν
F-
Br>Cl>F
Can you break a CCan you break a C--F bond? F bond? Only in special cases or conditionsOnly in special cases or conditions
Overall Atmospheric Chemistry of FTOHs
C
C
FF
F
CO
HF
HH
HH
FTOH
FF
F
C
C
FF
F
CO
FH
H
FF
F
H
C
C
FF
F
OF
FF
F
H
C
C
FF
F
OF
FF
F
O O•
C
O
FF
FF
FF
F
O•
C
C
FF
F
+OH/-H2O
xPerfluoroAldehyde
F
+O2/-HO2
FF
F
x
FT-Aldehyde
x
x
CO
n
•
FFn
CO2
+OH/-H2O +O2
+NO/-NO 2 +O2
+NO/-NO 2
Lifetime = 20 d Lifetime = 20 d Lifetime = 30 d
"Unzipping"
C
C
FF
F
OF
FF
F
OH
C
OH
FF
FF
FF
FC
CO
FF
F
FF
FC
CO
FF
x
n n
HO
FF
F n
PFNA (x=6)
PFOA (x=6)
+HOO/-O3
+ROO/-R'CHO-HF+H2O/-HF
"Novel" atmospheric chemistry
Do the Do the SulfamidoethanolsSulfamidoethanols Degrade to Acids in the Atmosphere?Degrade to Acids in the Atmosphere?
Alternative source of PFCAs?Alternative source of PFCAs?
F F
F F
F FS
FF FO
ON
CH3
CH2CH2OH F F
F F
F FS
FF FO
ON
CH3
CH2 CO
H
F F
F F
F FS
FF FO
ON
CH3
H
F F
F F
F FS
FF FO
ON
H
CH2CH2OH
F F
F F
F FS
FF FO
ON
CH2CH3
CH2CH2OHOH
C
F F
F F
F F
FF F
F F
F F
F F
ORS
•
•FF F
MethylFBSE
O
O
Alcohol Oxidation
N-Dealkylation
OH
Addition
OR
PFCAs!!! ....experiments ongoing.
F F
F F
F FS
FF FO
O
•
+
•OH
•OH•OH
SO2
PFBS
Posters: ENV017 & 021Posters: ENV017 & 021
Hydrolysis? Hydrolysis?
R CF
HH
Why?• F- is a VERY poor leaving group;• Thus SN1 and SN2 only go slowly; • polyfluorination increases 'steric' issues;
O:H
F-Only Slowly
half-life (pH 7)
~30 yrs
50 daysHClH3PO4
HFBenzoic acidTFAPFOSPFOA
Low2.123.144.200.5Extremely Low~2
CH3F
(CH3)3CFCH3Br
(CH3)3CCl 23 sec
1 yrpKa
F F
F F
F FS
F FO
OO-
F
F
F
F
F
F
F
FF
CF F
F F
F FO-
F
F
F
F
F
F
F
FF
O
In the environment?
Likely as salts
Except in special casesExcept in special cases……where Fwhere F-- is pushed!is pushed!
C
O•
FFF
F
FF
F
CO
FFCC
FFF
FF
CC C
FFF
F
F
F
CC C
FFF
F
OHF
F
CC C
FFF
F
OHF
F
O CC C
FFF
OHF
FO
F•
•
•+
•
CC
FFF O
F
H2O CC
FFF O
HO
+ F-
HCO3- + 2F-
C
OH
FF
F
F
FF
F
C
CO
FF
F
FF
F
C
CO
FF
n
n
HO
FF
F n
C
C•
FF
F
F
FF
F n
C
C
FF
F
F
FF
F n
O O•O2
R-CH-O-O•
-HF
+H2O/-HF
C
C
FF
F
F
FF
F
R1 R2Atmospheric Reagents
{Reactive?
C
C
F
FF
F
F
FF n
O•
NO/NO2
CO
FF
Fate of Perfluorocarbon Radicals
MajorMajor low %low %
OH
CF3
O
CFF
C
C
FF
FF
FF
F
C
HH
O
OH
C
CC
FFF
FF
CF
OHO
H
F-
+ HF
Eliminat ion
H2O
Stable
α,β unsaturated acids
C
C
FF
FF
FF
F
C
HH
O
H
C
CC
FFF
FF
CF
OH
H + HFH2O
α,β unsaturated aldehydes
abiotic; x=6, pH 7, T=23C ~35 days
biotic (bacteria); x=6, pH 7, T=23C ~14 days
biotic (rats); x=6, pH 7.2, T=23C ~very fast
Biotic & Abiotic are much Faster
Telomer Acids
Telomer Aldehyde
x
x
β-Eliminat ionAcidic "H"
Acidic "H"
If the right ‘architecture’ then ELIMINATE?
*SEE Poster TOX008; is HF the cause of the high toxicity of 10:2*SEE Poster TOX008; is HF the cause of the high toxicity of 10:2 FTCA?FTCA?
**
FF
F F
F F
F F
F F
FF
FC
F F
CO
HF
F
HH
H
H
FF
F F
F F
F F
F F
FF
FC
F F
C
HH
FF
H
FF
F F
F F
F F
F F
FF
FC
F F
CO
HH
FF
OH
FF
F F
F F
F F
F F
FF
FC
F F
CO
OH
F
H
FF
F F
F F
F F
F F
FF
F C
F F
O
OH
-HF
8:2 FTOH
PFOA
8:2 FTOH Acid
8:2 FTOH α,β Acid [major product]
8:2 FTOH Aldehyde
β oxid
atio
n
Microbes
FF
F F
F F
F F
F F
FF
FC
F F
CO
H
α,β 8:2 FTOH Aldehyde
F
H
O
slow
Microbial Metabolism Pathway ~
Posters: ENV011 & 022Posters: ENV011 & 022
Rat Liver Metabolism Pathway ~
NoteNote: important that PFNA (odd PFCA) : important that PFNA (odd PFCA) is, at most, a minor component.is, at most, a minor component.
FF
F F
F F
F F
F F
FF
FC
F F
COHF
F
HH
H
H
FF
F F
F F
F F
F F
FF
FC
F F
C
HH
FF
H
FF
F F
F F
F F
F F
FF
FC
F F
CO
HH
FF
OH
FF
F F
F F
F F
F F
FF
FC
F F
CO
OH
F
HFF
F F
F F
F F
F F
FF
F C
F F
O
OH
O
FF
F F
F F
F F
F F
FF
FC
F F
FF
8:2 FTOH
PFOA
Conjugates...8:2 FTOH Acid
8:2 FTOH α,β Acid
8:2 FTOH Aldehyde
O
OH
Liver cells
α,β 8:2 FTOH Aldehyde
PFNA (minor)
β oxidation
α oxidation
FF
F F
F F
F F
F F
FF
FC
F F
CO
H
F
H
slow
Major
-HF
-HF
GST
GSTGlutathione Adducts
Glutathione Adducts
Hagen, Belisle, et al, 1981. Anal Biochem. 118:336-343; Martin, JW, SA Mabury,and PJ O’Brien. 2005. Metabolic Products and Pathways of FluorotelomerAlcohols in Isolated Rat Hepatocytes. Chemico-Biological Inter. In press .Posters: TOX010Posters: TOX010
FF
F F
F F
F F
F F
FF
FC
F F
CO
OH
F
H
FF
F F
F F
F F
F F
FF
F C
F F
O
OH
PFOA
slow
Why is this reaction so slow?
• OH or FeO+ are strong electrophiles but...
...the β carbon is relatively electron deficient!
Thus is it surprising the β carbon is reactive towards nucleophiles?
FF
F F
F F
F F
F F
FF
FC
F F
CO
H
F
HFAST
G-S-H• •• •
FF
F F
F F
F F
F F
FF
FC
F F
CO
H
S
H
CH2
CHCOOH
NH C CH3O
"Mercapturate"
NO! One hopes it is GSH and not one of the nucelophilic centres on a protein or in DNA.
Where does this go?
FF
F F
F F
F F
F F
FF
FS
F F
FF Conjugates...
O
ON
CH2CH3
CH2CH2OH
FF
F F
F F
F F
F F
FF
FS
F F
FF
O
ON
CH2CH3
CH2COOH
FF
F F
F F
F F
F F
FF
FS
F F
FF
O
ON
H
CH2CH2OH
FF
F F
F F
F F
F F
FF
FS
F F
FF
O
ONH2
FF
F F
F F
F F
F F
FF
FS
F F
FF
O
OO-
PFOS
FF
F F
F F
F F
F F
FF
FS
F F
FF
O
ON
H
CH2COOH
Conjugates...
Conjugates...
Human & Rat Biotransformation of EthylFose
XuXu et al, 2004. Chem. Res. et al, 2004. Chem. Res. ToxicolToxicol. 17: 767. 17: 767--775; 775; TomyTomy et al. 2004. ES&T (Fish Livers)et al. 2004. ES&T (Fish Livers) Posters: ENV006, 014, 015, Posters: ENV006, 014, 015,
No Reactions @ EnvironmentallyRelevant Conditions....even examplesunder 'extreme conditions' are rare orhard to decipher.
F F
F F
F FS
F FO
OO-
F
F
F
F
F
F
F
FF
C
F F
F F
F FO-
F
F
F
F
F
F
F
FF
O
F3C CO
O–
Engineered "bioreactor"
over 90 days
Measured evolution of F-
Kim et al, 2000. Env Eng Sci. 17:
One persuasive example:
Okay but what about those perfluorinated acids Okay but what about those perfluorinated acids that are all the rage?that are all the rage?
YesYes……pretty boring indeed with respect to Reactions!pretty boring indeed with respect to Reactions!
fX fθ
X-F -0.38
0.06
0.20
0.59
-1.11
-5.19
-1.64
0.37
0.94
1.09
1.35
-0.03
-4.13
-0.44
X-Cl
X-Br
X-I
X-COOH
X-COO-
Kow Fragments
Hansch & Leo; EOC 1st Edition
X-OH
Kow Correction Factors "electronic effects"
Nearby Polyhalogenation
2 on same C3 on same C2 on adjacent single-bonded C3 on adjacent single-bonded Cand so forth...
0.601.590.280.56
F
CH2 FCF2F3C
Water SolubilityKow
1∝
C
F F
F F
F FO-
F
F
F
F
F
F
F
FF
O
Water Solubility and PartitioningWater Solubility and Partitioning
CarboxylatesPFC8 PFC10 PFC11 PFC12 PFC14 PFS8 PFS6
BCF
1e+0
1e+1
1e+2
1e+3
1e+4
1e+5
Sulfonates
CarcassLiverBlood
Martin, J., S.A. Mabury, K.S. Solomon, D.C.G. Muir. 2003 Bioconcentration and Tissue Distribution of Perfluorinated Acids in Rainbow Trout (Oncorhynchus mykiss Environ. Tox. Chem. 22: 189-195.
Martin, J., S.A. Mabury, K.S. Solomon, D.C.G. Muir. 2003 Dietary Accumulation of Perfluorinated Acids in Rainbow Trout (Oncorhynchus mykiss. Environ. Tox. Chem. 22:196-204.
BCF=ku/kd
Additional CF2 results in a ~7x increase in the BCF.
BCF/BAF of PFCAs
fX fθ
X-F 0.07
-0.79
-1.18
-0.20
-1.89
-3.47
-3.67
0.21
-0.53
-0.84
0.32
-2.63
na
-4.69
X-Cl
X-Br
X-CF3
X-CBr3
X-CCl3
X-COOH
V.P. Fragments
Simmons; 1999. JAFC; 47:1711-1716
Henry's Law Fragments
Hine & Mookerjee 1975 in EOC 1st Edition
fX fθ
C-F +0.50
-0.30
-0.87
-3.21
-3.10
+0.14
-0.21
-1.83
C-Cl
C-Br
C-NO2
C-OH
Fluoros Flying?
FF
FF
FF
FF
FF
8:2 FTOH
Cl8-Dioxin
PCB 153
Di-(2-ethylhexyl) pthalate
n-Decane
CBr3H
1,2 Dichlorobenzene
Ethoxybenzene
CH2CH2OH
FF
F
FFF
F
M.W.
464 460
360
390
142
252
147
122
V.P. (Pa)
212* 0.0000000001
0.0001
0.0019
173
724
200
204
Data from "EOC" Schwarzenbach et al ; *Data from Lei, Mabury, et al, unpublished data.
8:2 FTOH by V.P. and M.W.
So are Fluorocarbons very Polarizable? NO!
FF
F F
F F
F F
F F
FF
F
F
F F
F
M.W. R.I.1 Density1 M2 V.P. α5
438 1.282 1.766 155 46773 15.2
(cm3/mole)
α = polarizabilityR.I. = Refractive IndexM = Molar Volume
1Aldrich; 2McGowan et al; 3CRC Online;4Schwarzenbach5Calculated with Gaussian by M. Staikova; *for C10Cl6H16
(Pa)
HH
H H
H H
H H
H H
HH
H
H
H H
H
114 1.398 0.703 124 18194 15.8
ClCl
Cl Cl
Cl Cl
Cl Cl
Cl Cl
ClCl
Cl
Cl
Cl Cl
Cl
"make believe molecule"
Per...Octanes
890 ????? ????? ? 10-3 * 47.1
H
F
Cl
A30
FluoroAlcohol Physical Properties
]]RR22=0.99=0.99
P (Pa) Log Kaw Log Koa Csat Log Kow
4:2 FTOH6:2 FTOH8:2 FTOH10:2 FTOHNEtFosaNMeFoseNEtFose
1670; 992; 489(a) 876; 713; 107(a) 227; 254; 2;4(b) 53; 144; 0.7(a) 7; 0.240.7;0.00040.35; 0.0017; 0.79
1.8 1.7 1.3
3.33.64.24.85.96.87.1
148
w
2.03.34.92.74.1
?
Stock et al 2004. ES&T. 38:1693-1699; Lei et al, 2004. J Chem Eng Data 49:1013-1022; 25CKrusic et al, J Phys Chem A; 2005; 109:6232-6241; (a) calculated at 35C; (b) calculated at 21C; Schoeib et al, 3M Values OPPT DocsBonin, Lau, Ellis, & Mabury, unpublished data.
SummarySummary……major points:major points:
•• OrganofluorinesOrganofluorines are intriguing ~ lots to learn and interesting science to do;are intriguing ~ lots to learn and interesting science to do;
•• They are generally highly persistent because of inductive effecThey are generally highly persistent because of inductive effects of Fts of Fand the and the ‘‘poor leaving grouppoor leaving group’’ ability of Fability of F--; Perfluorinated acids ; Perfluorinated acids could could ‘‘redefine persistenceredefine persistence’’;;
•• Breakage of CBreakage of C--F bonds requires specific conditions;F bonds requires specific conditions;
•• Polyfluorinated compound are highly volatile with respect to maPolyfluorinated compound are highly volatile with respect to mass;ss;
•• Longer chain Perfluorinated compounds are moderately Longer chain Perfluorinated compounds are moderately bioaccumulativebioaccumulative;;
•• Appropriate to treat acids such as PFOS, PFOA, etc as degradatiAppropriate to treat acids such as PFOS, PFOA, etc as degradation products;on products;
•• Intermediates in the conversion of Intermediates in the conversion of FluoroalcoholFluoroalcohol to to PFAcidsPFAcids are are worth worth invesigationinvesigation;;
•• As a first step in solving As a first step in solving ““the problemthe problem”” address address ‘‘residualresidual’’ materials;materials;
•• Chemical Architecture mattersChemical Architecture matters……watch out for large, perfluorinated watch out for large, perfluorinated chemicals that do not react with OH in the atmosphere ~ GWP issuchemicals that do not react with OH in the atmosphere ~ GWP issues.es.
n
FF
FF
FF
FF
FF
FF
FF
F
S
"Fluoro- Monomer"
F
"Fluorinated Polymer"
F
OCO
C CH
HH3C
OCO
CCH3
CH2 CC
CH3
OO
CH2
m
OON
H3C CH2H2C
OH
"MethyFose Alcohol"
FF
FF
FF
FF
FF
FF
FF
F
S
FF OO
NH3C CH2
H2C
FF
FF
FF
FF
FF
FF
F
FF
S
FF
O
O
NH3C
CH2H2COH
FF
FF
FF
FF
FF
FF
FF
F
S
FF OO
NH3C CH2
H2CH2C
CH2
H2C(CH2)x
H2CCH3
FF
FF
FF
FF
FF
FF
FF
F
S
FF OO
O-
PFOS
Atmosphere
"Residual" 1-3 % OH Rxns
Biological Rxns
Human Exposure?
"Intermediates"
PolyFluoroPolyFluoro SulfamidoethanolsSulfamidoethanols…….Big Picture.Big Picture
n
FF
FF
FF
FF
FF
FF
FF
F
CH2
"Fluoro- Monomer"
F
"Fluorinated Polymer"
F
COC C
H
HH3C
COCCH3
CH2 CC
CH3
OO
CH2
m
CH2
8:2 FTOH(and relateds)
H2CCH2
H2C(CH2)x
H2CCH3
FF
FF
FF
FF
FF
FF
FF
F
FF
PFOA, PFNA, etc (Atmo) PFOA (bio)
Atmosphere
"Residual" 1-3 % OH Rxns
Biological Rxns
Human Exposure?
"Intermediates"
HO
FF
FF
FF
FF
FF
FF
FF
F
CH2
FF
CH2O
FF
FF
FF
FF
FF
FF
FF
F
CH2
FF
H2CO
FF
FF F
F
FF F
F
FF
F
FF
CH2
FF
CH2HO
CO OH
C
FF
FF
FF
FF
FF
FF
FF
F
OOH
Differences? More is known (published); potential for longer chain PFCAs from larger FTOHs.
FinaleFinale……the FTOH Fatethe FTOH Fate
Grad Students: Tim Boudreau, Naomi Stock, Wai Chi Kwan, Kiet Chau, Yun Ye, Marla Smithwick, Hans Sanderson, Amila DeSilva,Suzanne Gauthier, Joyce Dinglasan,Craig Butt, Jessica Currie, CoraYoung, Michelle MacDonald, Robert Dumoulin
Post-Docs: Cheryl Moody, David Ellis, Jon Martin, Sean Richards,Charles Wong, Stella Mello, Vasile Furdui
Undergraduate Students: Ryan Sullivan, Stacy Economou, Lisa Deeleebeck, Julia Bonin, Sandy Williams, Erin Marchington
Research Staff: Ying Lei, Dan Mathers
Funding: NSERC operating, strategic (3 yrs), equipment; 3M; Telomer Research Program (1 yr), Omnova Foundation (2 yrs)
Collaborators:Derek Muir; Elizabeth Edwards; Brian Scott, Peter O’Brien, Keith Solomon, & Paul Sibley; Kim Strong; Frank Wania;
Tim Wallington, Mike Hurley, & Mads Sulbaek Andersen et alFord Motor Company
Co-authors, Collaborators, & Funding